JPH05333467A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain an image high in contrast and superior in quality by using a developing solution high in stability and to reduce black spots by incorporating a specified nucleator in a silver halide emulsion layer and a specified compound in an emulsion layer and/or a hydrophilic colloidal layer. CONSTITUTION:The silver halide emulsion layer contains the nucleator represented by formula I and the emulsion layer and/or the adjacent hydrophilic colloidal layer containing no silver halide emulsion layer contains the compound represented by formula II or III. In formulae I-III, R1 is an aliphatic or aromatic group; R2 is H or alkyl or the like; G1 is -CO-, -SO2-, etc., each of A1 and A2 is H, or one of them is H and the other is optionally substituted alkylsulfonyl or the like; R in formula II is an aliphatic or aromatic group, etc.; Z is an atomic group necessary to form an N-containing hetero-cyclic group; R in formula III is an aromatic group; and B is phenyl or naphthyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a super-high contrast negative image forming method using the same, and in particular, a useful photographic group can be made available in a development processing step. The present invention relates to a silver halide photographic light-sensitive material containing a compound and a compound for fully utilizing the characteristics of the compound.

[0002]

2. Description of the Related Art In the field of silver halide photographic materials for photolithography, in order to cope with the variety and complexity of printed matter, a photographic light-sensitive material having good original reproducibility, a stable processing solution, or a simple replenisher There is a request for conversion. Especially in the line drawing process, manuscripts are typeset characters, handwritten characters,
It is made by pasting illustrations and half-tone dots. Therefore, the originals contain images with different densities and line widths, and the plate-making camera that reproduces these originals well
A photographic light-sensitive material or an image forming method is strongly desired. On the other hand, halftone pictures are enlarged (expanded) or reduced (closed) widely in the production of catalogs and large posters, and in the production of enlarging halftone dots, the number of lines becomes rough and blurred. Will be taken. For reduction, the number of lines /
Inch is large and thin. Therefore, an image forming method having a wider latitude is required to maintain the reproducibility of halftone.

A halogen lamp or a xenon lamp is used as a light source for a plate making camera. In order to obtain photographing sensitivity with respect to these light sources, the photographic light-sensitive material is usually ortho-sensitized. However, ortho-sensitized photographic materials are more strongly affected by the chromatic aberration of the lens,
Therefore, it has been found that the image quality is likely to deteriorate. Further, this deterioration becomes more remarkable for the xenon lamp light source.
As a system that meets the demand for a wide latitude, a lithographic silver halide light-sensitive material made of silver chlorobromide (at least a silver chloride content of at least 50%) has an extremely low effective concentration of sulfite ion (usually 0.1 mol / mol). There is known a method of obtaining a line image or a halftone dot image having a high contrast and a high blackening density in which an image portion and a non-image portion are clearly distinguished by processing with a hydroquinone developer. However, with this method, the concentration of sulfurous acid in the developer is low, so development is extremely unstable against air oxidation, and various efforts and efforts have been made to maintain stable solution activity. The current situation is that the work efficiency is lowered due to the extremely slow speed.

For this reason, the instability of image formation due to the above-mentioned developing method (lith development system) is eliminated, and the image is developed with a processing solution having good storage stability to obtain an image having super-high contrast photographic characteristics. A forming system is desired, one of which is US Pat. Nos. 4,166,742 and 4,168,9.
77, 4,221,857, 4,224,40
1, No. 4,243,739, No. 4,272,606
No. 4,311,781, a surface latent image type silver halide photographic light-sensitive material containing a specific acylhydrazine compound is added at a pH of 11.0 to 12.3 with a sulfite preservative. A system has been proposed which forms a super-high contrast negative image having a γ of more than 10 by processing with a developer containing 15 mol / liter or more and having good storage stability. This new image forming system can only use silver chlorobromide, which has a high silver chloride content in conventional super-high contrast image formation, whereas silver iodobromide and silver chloroiodobromide can also be used. There is. The above image system has sharp dot quality,
Although it exhibits excellent performance in terms of process stability, rapidity, and original reproducibility, a system with improved original reproducibility is desired in order to cope with the recent variety of printed materials.

As an attempt to improve the image quality, for example, a method of releasing a development inhibitor like a silver image from a redox compound having a carbonyl group disclosed in JP-A-61-213847 is known. However, even when these compounds are used, the halftone expansion is insufficient. Therefore, there has been a demand for the development of a light-sensitive material capable of forming a high-density halftone dot image using a stable developing solution and having a wide image tone control. On the other hand, in the work of the plate collection and reversion process, it has been attempted to improve the work efficiency by performing the work in a brighter environment. Therefore, it is necessary to deal with it in an environment that can be called a bright room. The development of photosensitive materials for plate making and the development of exposure printers have been promoted. The bright room light-sensitive material described in this patent is a light-sensitive material that can be safely used for a long time as light having a wavelength of 400 nm or more that does not contain an ultraviolet light component and is safelight.

The light-sensitive material for the bright room used in the plate collecting and reversing process is a developed film having characters or halftone images formed thereon as an original, and these originals and the reversible photosensitive material are contact-exposed and exposed. It is a light-sensitive material used for negative image / positive image conversion or positive layer / positive image conversion. A halftone dot image, a line image and a character image are negative according to their halftone dot area, line width and character image width. It is required to have the ability to convert images / positive images. It is required to have the ability to adjust the tone of halftone images and the line width of character / line images. Came. However, in the advanced image conversion work of forming a blank character image by overlapping, the conventional method by the bright room return process using the light room photosensitive material is performed by the conventional dark room return process using the dark room return light photosensitive material. Compared with the method, there was a drawback that the quality of the extracted character image deteriorates.

A more detailed description of the method of forming a blank character image by overlapping and reversing is given in JP-A-2-29.
As shown in FIG. 1 of Japanese Patent No. 3736, transparent or translucent sticking bases (a) and (c) (usually 100
A polyethylene terephthalate film having a thickness of about μm is used) and a film (line drawing original) (b) on which a character or line image is formed and a halftone dot original film (b) on which a halftone image is formed. ) Is attached to form an original, and the emulsion surface of the light-sensitive material for return (e) is brought into close contact with the halftone original of (d) to perform exposure. Post-exposure development processing is performed to form a white blank portion of the line drawing in the halftone dot image. An important point in such a method of forming a blank character image is ideally that the negative image / positive image conversion is performed according to the halftone dot area and the line width of each halftone original and line drawing original. However, as is apparent in FIG. 1, halftone dot originals are exposed by directly contacting them with the emulsion surface of the light-sensitive material for return, whereas line drawing originals are embedded base (c) and halftone originals (ni. ) Will be exposed to the return light-sensitive material through the middle. For this reason, if an exposure amount that faithfully converts a halftone image to a negative image / positive image is given, the line drawing original becomes out-of-focus exposure through the spacer by the embedding base (C) and the halftone original (D). The line width of the white part of the line becomes narrow. This is the reason that the quality of the extracted character image deteriorates. Systems using hydrazine to solve the above problems are disclosed in JP-A-62-80640 and JP-A-62-235938.
No. 62-235939, No. 63-104046.
No. 63-103235, No. 63-296031.
No. 63-314541, No. 64-13545,
However, it is not sufficient and further improvement is desired.

An example of a system using hydrazine containing a redox compound which releases a development inhibitor upon being oxidized is disclosed in JP-A-61-213847 and 64-7214.
No. 0, Japanese Patent Application Nos. 1-108216, 1-144721
Nos. 1-113094, 1-130981, 1-250004, etc. In this way, by using a redox compound that releases a development inhibitor by being oxidized with a nucleating agent, in a photographic light-sensitive material, the reproducibility of halftone dots such as stretch and shrinkage, and fine line or fine line The image quality such as missing is improved. Further, in the reversing sensitive material, the image quality improvement as described above has been attempted. On the other hand, on the other hand, a sensitive material using a nucleating agent has an adverse effect that black spots are generated particularly in an air-oxidized fatigue developing solution, and its characteristics are not fully utilized. Therefore, various means have been studied as means for reducing the occurrence of black spots. For example, JP-A-2-31055 discloses a method for improving the content by containing a trihydroxybenzene derivative in a light-sensitive material.
5 are disclosed. Further, the improvement by incorporating a hydroquinone derivative into a light-sensitive material is disclosed in Japanese Patent Application No. 02-1
27480. These means have the drawbacks of decreasing the efficacy and increasing the number of black spots due to the passage of time of the light-sensitive material, etc., and are not sufficient yet, and further improvements are desired.

[0009]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide a photosensitive material for plate making which can obtain a high contrast image by using a highly stable developing solution. An object of the present invention is to provide a photographic material for plate making which has excellent image quality such as stretching, contraction, copy dots, and fine line reproducibility and has few black spots.

[0010]

The objects of the present invention have been achieved by the following silver halide photographic light-sensitive materials:
A hydrophilic layer having a silver halide emulsion layer containing at least one nucleating agent represented by the following general formula (N-1) on a support and not containing the layer and / or a silver halide emulsion adjacent thereto. This is achieved by a silver halide photographic light-sensitive material characterized in that the colloidal layer contains a compound represented by the following general formula (Q-1) or (Q-2). General formula (N-1)

[0011]

[Chemical 8]

[0012]

[Chemical 9]

First, the general formula (N-1) will be described in detail. In the formula, R ₁ represents an aliphatic group or an aromatic group,
R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydrazino group, a carbamoyl group or an oxycarbonyl group, and G ₁ represents-.
CO- group, -SO ₂ - group, -SO- group, -P (O) (R
₂ ) -group, -COCO- group, thiocarbonyl group or iminomethylene group, both A ₁ and A ₂ are hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted group. It represents a substituted arylsulfonyl group or a substituted or unsubstituted acyl group.

In the general formula (N-1), the aliphatic group represented by R ₁ is preferably an aliphatic group having 1 to 30 carbon atoms, particularly a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms. The group, here a branched alkyl group, may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, a carbonamide group or the like. The aromatic group represented by R ₁ in formula (N-1) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group is monocyclic or 2
It may be condensed with a ring aryl group to form a heteroaryl group. For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, and among others, a ring containing a benzene ring is preferable. Particularly preferred as R ₁ is an aryl group. The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and typical examples of the substituent include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, and a ureido group. Group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl Group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, diacylamino group, imide group,

[0015]

[Chemical 10]

Examples of preferred substituents include linear, branched or cyclic alkyl groups (preferably having 1 to 20 carbon atoms) and aralkyl groups (preferably having 1 to 3 carbon atoms in the alkyl moiety). Ring or bicyclic), alkoxy group (preferably having 1 to 20 carbon atoms), substituted amino group (preferably amino group substituted with alkyl group having 1 to 20 carbon atoms), acylamino group (preferably carbon) Having 2 to 30 carbon atoms, sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (preferably having 1 carbon atoms) ~ 30) and the like.

The alkyl group represented by R ₂ in the general formula (N-1) is preferably an alkyl group having 1 to 4 carbon atoms, for example, a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a sulfo group, Alkoxy group, phenyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or arylsulfonyl group, sulfamoyl group, nitro group, heteroaromatic ring group,

[0018]

[Chemical 11]

It may have a substituent such as, and these groups may be further substituted. The aryl group is preferably a monocyclic or bicyclic aryl group, and includes, for example, a benzene ring. This aryl group may be substituted, and examples of the substituent are the same as in the case of the alkyl group. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, which may be substituted with a halogen atom, an aryl group or the like. The aryloxy group is preferably a monocyclic one, and the substituent includes a halogen atom and the like. As the amino group, a ham-substituted amino group, an alkylamino group having 1 to 10 carbon atoms and an arylamino group are preferable, and the amino group may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group or the like. The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group or the like. The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or an aryloxycarbonyl group,
It may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group or the like.

Among the groups represented by R ₂ , when G ₁ is a carbonyl group, preferred is a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-
Hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (eg, o-hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-methane) Sulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group and the like), and a hydrogen atom is particularly preferable.

When G ₁ is a —SO ₂ — group, R ₂
Are preferably an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group), or a substituted amino group (eg, dimethylamino group). G
_{When 1} is a —SO— group, preferred R ₂ includes cyanobenzyl group, methylthiobenzyl group, etc., and G ₁ is

[0022]

[Chemical formula 12]

In the case of, R ₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group or a phenyl group, and particularly preferably a phenoxy group. G ₁ is N-
In the case of a substituted or unsubstituted iminomethylene group, preferred R
₂ is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group. As the substituent of R _2, the substituents listed for R ₁ can also be applied. As G in the general formula (I), -C
Most preferred is the O-group. Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ₁ -R ₂ moiety of atoms Specifically, it can be represented by the general formula (a).

[0024] In the general formula (a) -R ₃ -Z ₁ formula, Z ₁ is nucleophilically attacked to G _1, G ₁ -R ₃ -
A group capable of Z ₁ portion was split from the remaining molecule, R ₃ is one obtained by removing one hydrogen atom from R _2, Z ₁ is a nucleophilic attack to G _1, in G _1, R _3, Z ₁ A cyclic structure can be generated. More specifically, Z ₁ is represented by the general formula (N-1).
When the hydrazine compound of ₁ produces a next reaction intermediate due to oxidation or the like, it easily undergoes a nucleophilic reaction with G ₁ to convert R ₁ -N = N-G ₁ -R ₃ -Z ₁ R ₁ -N = N group to G 1 _A group capable of being cleaved from ₁ , specifically, OH, SH or NHR ₄ (R ₄ is a hydrogen atom, an alkyl group, an aryl group, —COR ₅ or —SO ₂ R
₅ , R ₅ is a hydrogen atom, an alkyl group, an aryl group,
It may be a heterocyclic group or the like, or a functional group which directly reacts with G ₁ such as COOH (here, OH, S
H, NHR ₄ , and -COOH may be temporarily protected so as to generate these groups by hydrolysis of alkali etc.), or

[0025]

[Chemical 13]

(Wherein R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group), a nucleophile such as a hydroxide ion or a sulfite ion is reacted to produce G It may be a functional group capable of reacting with ₁ . The ring formed by G ₁ , R ₃ and Z ₁ is preferably a 5-membered or 6-membered ring. General formula (a)
Among the compounds represented by, preferred examples include those represented by the general formulas (b) and (c). General formula (b)

[0027]

[Chemical 14]

In the formula, R ¹ _{b to} R ⁴ _b are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms), aryl groups (preferably C6 to C12) and the like, and may be the same or different. B is an atom necessary to complete a 5- or 6-membered ring which may have a substituent, and m, n
Is 0 or 1 and (n + m) is 1 or 2.
The 5- or 6-membered ring formed by B is, for example, a cyclohexene ring, a cyclopentene ring, a benzene ring, a naphthalene ring, a pyridine ring or a quinoline ring. Z ₁ has the same meaning as in formula (a). General formula (c)

[0029]

[Chemical 15]

In the formula, R _c ^{1 and} R _c ² represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom or the like, and may be the same or different. R _c ³ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. p represents an integer value of 0 to 2, and q represents 1 to 4.
R _c ¹ , R _c ² and R _c ³ may combine with each other to form a ring as long as Z ₁ has a structure capable of intramolecular nucleophilic attack on C ₁ . R _c ¹ and R _c ² are preferably a hydrogen atom, a halogen atom or an alkyl group, and R _c ³ is preferably an alkyl group or an aryl group. q is preferably 1 to 3, when q is 1, p is 1 or 2; when q is 2, p is 0 or 1; when q is 3, p is 0 or 1; Or when 3, there are multiple (CR
_c ¹ R _c ² ) may be the same or different. Z ₁ has the same meaning as in formula (a).

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group or the sum of Hammett's substituent constants is-).
Phenylsulfonyl group substituted to be 0.5 or more), acyl group having 20 or less carbon atoms (preferably benzoyl group, or substituted so that the sum of Hammett's substituent constants is -0.5 or more) A benzoyl group, or a linear or branched or cyclic unsubstituted and substituted aliphatic acyl group (as a substituent, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group,
Examples thereof include sulfonic acid groups. ) A hydrogen atom is most preferable as A ₁ and A ₂ .

R ₁ or R ₂ of the general formula (N-1) may have a ballast group or a polymer incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties.
It can be selected from phenoxy group, alkylphenoxy group and the like. Further, as the polymer, for example, JP-A-1-
The thing described in 100530 is mentioned.

R ₁ or R _{2 in the} general formula (N-1) may be one in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. As such an adsorption group,
US Pat. No. 4,385,10 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group and triazole group.
8, No. 4,459,347, JP-A-59-195,
No. 233, No. 59-200, No. 231, 59-20
1,045, 59-201, 046, 59-2
01,047, 59-2, 201,048, 59-
No. 201,049, JP-A Nos. 61-170,733, 61-270,744, 62-948, and Japanese Patent Application No.
2-67,508, 62-67,509, 62
The groups described in -67,510 are mentioned. Specific examples of the compound represented by formula (N-1) are shown below. However, the present invention is not limited to the following compounds.

[0034]

[Chemical 16]

[0035]

[Chemical 17]

[0036]

[Chemical 18]

[0037]

[Chemical 19]

[0038]

[Chemical 20]

[0039]

[Chemical 21]

[0040]

[Chemical formula 22]

[0041]

[Chemical formula 23]

[0042]

[Chemical formula 24]

[0043]

[Chemical 25]

[0044]

[Chemical formula 26]

[0045]

[Chemical 27]

[0046]

[Chemical 28]

[0047]

[Chemical 29]

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,207.
Issue 4, Issue 4,269,929, Issue 4,276,364
No. 4, ibid. 4,278,748, ibid. 4,385,108
Nos. 4,459,347 and 4,560,638.
No. 4,478,928, British Patent No. 2,011,3
91B, JP-A Nos. 60-179734 and 62-27.
0,948, 63-29,751, 61-17
0,733, 61-270,744, 62-9.
48, EP 217,310, or US 4,68
6,167, JP-A-62-178,246, 63.
-32,538, 63-104,047, 63
-121,838, 63-129,337, 6
3-223,744, 63-234,244, 63-234,245, 63-234,246,
63-294,552, 63-306,438.
No. 1,100,530, 1,105,94.
No. 1, 1,105,943, JP-A-64-10,2
No. 33, JP-A-1-90,439, Japanese Patent Application No. 63-10
No. 5,682, No. 63-114, No. 118, No. 63-1
No. 10,051, No. 63-114, 119, No. 63-
116, 239, 63-147, 339, 63
-179,760, 63-229,163, Japanese Patent Application Nos. 1-18,377, 1-18,378, 1-
18,379, 1-15,755, 1-16,
No. 814, No. 1-40, 792, No. 1-42, 615
No. 1-42,616, No. 1-123,693,
No. 1-126,284, U.S. Pat. No. 4,988,604.
It is possible to use those described in No.

The nucleating agent of the present invention is 1 × 10 ^{−6 to} 5 × 10 ⁻¹ , more preferably 1 × 10 ⁶ per mol of silver halide.
It is used within the range of ^-5 to 1 x 10 ^-1 mol. The nucleating agent of the present invention is a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide,
It can be used by dissolving it in methyl cellosolve or the like.
In addition, by well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Also, poly tert butyl acrylamide,
It is also possible to dissolve it together with a polymer such as polymethylmethacrylate or polyvinyl acetate, the above-mentioned auxiliary solvent, and optionally the above-mentioned oil or the like to mechanically prepare an emulsified dispersion for use. Alternatively, the redox compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method. In the case of using it as an emulsified dispersion, it may be preferable to remove the auxiliary solvent (by heating under reduced pressure distillation, ultrafiltration, Nudel water washing, etc.), if necessary.

The compound represented by formula (Q-1) of the present invention will be described. In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group, and Z represents an atomic group necessary for forming a nitrogen-containing heteroaromatic ring.

The compound represented by formula (Q-1) will be described in more detail below. In the general formula (Q-1), the aliphatic group represented by R is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. As the heterocyclic group (heterocycle) of R, N,
3 to 10 containing at least one of O and S atoms
Membered saturated or unsaturated heterocycle, which may be a monocycle or may form a condensed ring with another aromatic or heterocycle. The heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, for example,
Those containing a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazoline group and a benzthiazolyl group are preferable. Preferred as R is an aromatic group.

R may be substituted with a substituent. Examples of the substituent include, for example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group. Groups, hydroxy groups, halogen atoms, cyano groups, sulfo groups and carboxyl groups, alkyl and aryloxycarbonyl groups, acyl groups,
In addition to an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a nitro group, an alkylthio group, an arylthio group and the like, groups represented by the following general formula (R) can be mentioned. General formula (R)

[0053]

[Chemical 30]

In the general formula (R), Y is --CO-- or --SO ₂
-, - P (O) ( R 3) - ( wherein R ₃ represents an alkoxy group or an aryloxy group.) Represent, L is a single bond, -O -, - S-, or -NR ₄ - (In the formula, R ₄ represents a hydrogen atom, an aliphatic group or an aromatic group). R
₁ and R ₂ represent a hydrogen atom, an aromatic group, an aliphatic group or a heterocyclic group, and may be the same or different, or may be bonded to each other to form a ring. R may contain one or more groups represented by the general formula (R).

In the general formula (R), the aliphatic group represented by R ₁ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The hetero ring of R ₁ is a 3- to 10-membered saturated or unsaturated hetero ring containing at least one of N, O, and S atoms, which may be a single ring, or other hetero ring. A condensed ring may be formed with an aromatic or hetero ring. The heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, a benzthiazolyl group. Those are preferable.

R ₁ may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted. For example an alkyl group,
Aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group , Sulfinyl groups, hydroxy groups, halogen atoms, cyano groups, sulfo groups and carboxyl groups, alkyl and aryloxycarbonyl groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, carbonamide groups, sulfonamide groups, nitro groups, alkylthio groups, And an arylthio group.
When possible, these groups may be linked to each other to form a ring.

The aliphatic group represented by R ₂ in the general formula (R) is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R ₂ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group. R ₂ may be substituted with a substituent. Examples of the substituent include those enumerated as the substituents of R ₁ in the general formula (R). If possible, R ₁ and R ₂ may be connected to each other to form a ring. R ₂ is more preferably a hydrogen atom.

Y in the general formula (R) is -CO.
-, - SO ₂ - is particularly preferred, L is a single bond and -N
R ₄ − is preferred. The aliphatic group represented by R ₄ in the general formula (R) is a linear, branched or cyclic alkyl group,
It is an alkenyl group or an alkynyl group. The aromatic group represented by R ₄ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group. R ₄ may be substituted with a substituent. Examples of the substituent include those enumerated as the substituents of R ₁ in the general formula (R). R ₄ is more preferably a hydrogen atom.

Further, R may have a group containing an adsorption promoting group for silver halide as a substituent. R is a substitutable adsorption-promoting group on silver halide, which can be represented by X- (L ') _t- , where X is an adsorption-promoting group on silver halide,
L'is a divalent linking group. t is 0 or 1. X
Preferred examples of the adsorption promoting group for silver halide represented by are a thioamide group, a mercapto group, a group having a disulfide bond and a 5- or 6-membered nitrogen-containing heterocyclic group. The thioamide adsorption promoting group represented by X is a divalent group represented by -CS-amino-, which may be a part of the ring structure or an acyclic thioamide group. Useful thioamide adsorption-promoting groups include, for example, U.S. Pat. Nos. 4,030,925 and 4,031,127.
No. 4,048,207, No. 4,245,037
Issue 4, Issue 4,255,511, Issue 4,266,013
And 4,276,364, and Research Disclosure No. 1
Volume 51 No. 15162 (November 1976), and Vol. 176, No. It can be selected from those disclosed in 17626 (December 1978). Specific examples of the acyclic thioamide group include, for example, thioureido group, thiourethane group, dithiocarbamic acid ester group and the like, and specific examples of the cyclic thioamide group include, for example, 4-thiazoline-2-thione and 4-imidazoline-2. -Thion, 2-
Thiohydantoin, rhodanine, thiobarbituric acid,
Tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3,4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione , Benzoxazoline-2
-Thione and benzothiazoline-2-thione, etc., which may be further substituted. The mercapto group of X is an aliphatic mercapto group, an aromatic mercapto group, or a heterocyclic mercapto group (when the carbon atom to which the —SH group is bonded is a nitrogen atom next to it, a cyclic thioamide group having a tautomer relationship with this) And specific examples of this group are the same as those listed above).

Examples of the 5-membered or 6-membered nitrogen-containing heterocyclic group represented by X include 5-membered to 6-membered nitrogen-containing heterocycles consisting of a combination of nitrogen, oxygen, sulfur and carbon. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine and the like. These may be further substituted with appropriate substituents. Examples of the substituent include those described as the substituent of R.

Among those represented by X, preferred are cyclic thioamide groups (ie, mercapto-substituted nitrogen-containing heterocycles such as 2-mercaptothiadiazole group,
3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4
-Oxadiazole group, 2-mercaptobenzoxazole group, etc.) or a nitrogen-containing heterocyclic group (for example, benzotriazole group, benzimidazole group, indazole group, etc.). Two or more X- (L ') _t -groups may be substituted and may be the same or different.

As the divalent linking group represented by L ',
It is an atom or atomic group containing at least one of C, N, S, and O. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-,-
S -, - NH -, - N =, - CO -, - SO 2 -, is made of a single or combination of such (may have these groups the substituent). As a specific example,
For example -CONH -, - NHCONH -, - SO 2 NH
-, - COO -, - NHCOO -, - CH 2 CH 2 SO
_{2 NH -, - CH 2 CH} 2 CONH -, - NHCONHCH 2 CH
_{2 CONH -, - CH 2 -} , - (CH 2) 2 -, - (CH 2) 3 -

[0063]

[Chemical 31]

And the like. These may be further substituted with appropriate substituents. As the substituent, those mentioned as the substituent of R can be mentioned.

Further, R may contain therein a ballast group which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is an organic group giving a molecular weight sufficient to prevent the compound represented by the general formula (Q-1) from substantially diffusing into another layer or the treatment liquid, and is an alkyl group, an aryl group or a heterocycle. And a combination of one or more groups, ether groups, thioether groups, amide groups, ureido groups, urethane groups, sulfonamide groups, and the like. The ballast group is more preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

In the general formula (Q-1), the heteroaromatic ring group formed by the nitrogen atom and Z is preferably a 5- or 6-membered ring,
It may be a monocycle, may be condensed with another ring, and may be substituted. Representative examples of preferred heteroaromatic rings include, for example, pyrrole, imidazole, pyrazole,
1,2,3-triazole, 1,2,4-triazole, tetrazole, 2-thioxathiazoline, 2-oxathiazoline, 2-thioxaxazoline, 2-oxoxazoline, 2-thioxaimidazoline, 2-oxaimidazoline , 3-thioxa-1,2,4-triazoline, 3-oxa-1,2,4-triazoline, 1,2-
Oxazoline-5-thione, 1,2-thiazoline-5-
Thione, 1,2-oxazoline-5-one, 1,2-thiazolin-5-one, 2-thioxa-1,3,4-thiadiazoline, 2-oxa-1,3,4-thiadiazoline, 2-thioxa- 1,3,4-oxadiazoline, 2
-Oxa-1,3,4-oxadiazoline, 2-thioxadihydropyridine, 2-oxadihydropyridine, 4
-Thioxadihydropyridine, 4-oxadihydropyridine, isoindole, indole, indazole, benzotriazole, benzimidazole, 2-thioxabenzimidazole, 2-oxabenzimidazole,
Benzoxazoline-2-thione, azaindenes, benzoxazoline-2-one, benzothiazoline-2-
Thione, benzothiazolin-2-one, carbazole,
Purines, carbolines, phenoxazines, phenothiazines, pyrazolopyridines at various condensed ring positions, pyrazolopyrimidines, pyrazolopyrroles, pyrazolopyrazoles, pyrazoloimidazoles, pyrazolooxazoles, pyrazolothiazoles, Pyrazolotriazoles,
Examples thereof include imidazolopyridines, imidazolopyridines, imidazolopyrroles, imidazoloimidazoles, imidazolooxazoles, imidazolothiazoles and imidazolotriazoles.

Further preferred heteroaromatic rings are, for example, pyrrole, imidazole, pyrazole, triazole,
Tetrazole, 2-thioxathiazoline, 2-thioxoxazoline, indole, indazole, benzotriazole, benzimidazole, 2-thioxa-1,
3,4-thiadiazoline, azaindene, 5-thioxa-tetrazoline, 2-thioxa-1,3,4-oxadiazoline, 3-thioxa-1,2,4-triazoline,
There are various condensed ring position pyrazolopyridines, pyrazoloimidazoles and the like, and particularly preferable are heteroaromatic rings having a pyrazole skeleton such as pyrazole, indazole and pyrazolopyridine.

These heterocyclic compounds may have a substituent. Examples of the substituent include a mercapto group, a nitro group, a carboxyl group, a sulfo group, a phosphono group, a hydroxy group, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group and an acylamino group. Group, sulfonylamino group, ureido group, urethane group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, halogen atom, cyano group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group , Carbonamide group, sulfonamide group, phosphonamide group and the like. Specific examples of the compound represented by formula (Q-1) are shown below.
However, the present invention is not limited to the following compounds.

[0069]

[Chemical 32]

[0070]

[Chemical 33]

[0071]

[Chemical 34]

[0072]

[Chemical 35]

[0073]

[Chemical 36]

[0074]

[Chemical 37]

[0075]

[Chemical 38]

[0076]

[Chemical Formula 39]

[0077]

[Chemical 40]

In addition to the above compounds, compounds useful in the present invention include those disclosed in JP-A-3-39953 and the like. The method for synthesizing the compound of the present invention is also described in detail in JP-A-3-39953. The addition amount of the compound represented by the general formula (Q-1) of the present invention is not particularly limited, but is in the range of 10 mol to 10 ⁻³ mol, preferably 1 mol to 10 ⁻² mol% per mol of the nucleating agent. Used in. The compound represented by formula (Q-2) of the present invention will be described. In the formula, R represents an aromatic group and B represents a phenyl group or a naphthyl group.
These phenyl groups or naphthyl groups may or may not have a substituent. The compound represented by formula (Q-2) will be described in more detail. In the general formula (Q-2), R has the same meaning as R in the general formula (Q-1).

R may be substituted with a substituent. Examples of the substituent include, for example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group. Groups, hydroxy groups, halogen atoms, cyano groups, sulfo groups and carboxyl groups, alkyl and aryloxycarbonyl groups, acyl groups,
In addition to an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a nitro group, an alkylthio group, an arylthio group and the like, the groups represented by the above general formula (R) can be mentioned.

B represents a substituted or unsubstituted phenyl group or naphthyl group. Examples of the substituent of B include those described above as the substituent of R. General formula (Q-
Specific examples of the compound represented by 2) are shown below. However,
The present invention is not limited to the following compounds.

[0081]

[Chemical 41]

[0082]

[Chemical 42]

[0083]

[Chemical 43]

[0084]

[Chemical 44]

The addition amount of the compound of the general formula (Q-2) of the present invention is the same as that of the compound of the general formula (Q-1).

The general formula (Q-1) and the general formula (Q
The method of adding the compound of -2) can be performed in the same manner as the method of the nucleating agent represented by the general formula (N-1). If necessary, it can be dissolved and added together with the nucleating agent, or can be used by coemulsifying with the nucleating agent. In the present invention, it is preferable to use, in addition to the nucleating agent represented by the general formula (N-1), a redox compound capable of releasing a development inhibitor by being oxidized in a developing solution. A redox compound capable of releasing a development inhibitor by being oxidized according to the present invention, wherein at least a part of the development inhibitor is eluted into a developing solution and reacts with a developing solution component to be a compound having a small inhibiting property. A possible redox compound will be described. The redox group of the redox compound is preferably hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines and reductones, and more preferably hydrazines.
A redox compound capable of releasing a development inhibitor by being oxidized according to the present invention, and at least a part of the development inhibitor is eluted into a developing solution and reacts with a developing solution component, and a compound having a small inhibiting property is changed. Hydrazines used as such a redox compound are preferably represented by the following general formula (R-1), general formula (R-2) and general formula (R-3). The compound represented by formula (R-1) is particularly preferable.

[0087]

[Chemical 45]

In these formulas, R ₁ represents an aliphatic group or an aromatic group. G ₁ is -CO- group, -COCO- group, -C
S- _{groups, -C (= NG 2 R 2} ) - group, -SO- group, -S
O ₂ - group or _{-P (O) (G 2 R} 2) - represents a group.
G ₂ is a simple bond, -O- group, -S- group or -N
Represents a (R ₂ )-group, R ₂ represents a group having the same definition as R ₁ or a hydrogen atom, and when plural R ₂ are present in the molecule, they may be the same or different. A ₁ and A ₂ represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. In the general formula (R-1), at least one of A ₁ and A ₂ is a hydrogen atom. A ₃ has the same meaning as A ₁ , or —CH ₂ CH
(A ₄₎ - represents the (Time) _t -PUG. A ₄ is a nitro group, a cyano group, a carboxyl group, a sulfonyl group, or -G ₁ -G ₂ -R ₁ (in this case, two -G in the molecule).
₁ -G ₂ -R ₁ may be the same or different. ) Is represented.

General formulas (R-1), (R-2), (R-
3) will be described in more detail. General formula (R-
In 1), (R-2), and (R-3), the aliphatic group represented by R ₁ is preferably one having 1 to 30 carbon atoms, and particularly a straight chain or branched one having 1 to 20 carbon atoms. Alternatively, it is a cyclic alkyl group. This alkyl group may have a substituent. In formulas (R-1), (R-2), and (R-3), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and an isoquinoline ring. Of these, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group for R ₁ may be substituted, and typical examples of the substituent include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group and a substituted group. Amino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group,
Examples of the halogen atom, a cyano group, a sulfo group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, and the like, as a preferable substituent, Linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), aralkyl group (preferably having 7 to 30 carbon atoms), alkoxy group (preferably having 1 to 30 carbon atoms), substitution Amino group (preferably amino group substituted with an alkyl group having 1 to 30 carbon atoms), acylamino group (preferably 2 to 4 carbon atoms)
0), sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms), phosphoric acid amide group (preferably having 1 to 40 carbon atoms) ) And so on.

General formulas (R-1), (R-2) and (R-
As G ₁ in 3), —CO— group and —SO ₂ — group are preferable, and —CO— group is most preferable. Preferably a hydrogen atom as A _1, A _2, as the A ₃ hydrogen atoms, -C
_{H 2 CH (A 4) -} (Time) t -PUG are preferred.

General formulas (R-1), (R-2) and (R-
In 3), Time represents a divalent linking group and may have a timing adjusting function. The divalent linking group represented by Time represents a group capable of releasing PUG from Time-PUG released from an oxidized product of a redox mother nucleus through a reaction in one step or more steps. Tim
Examples of the divalent linking group represented by e include, for example, U.S. Pat. No. 4,248,962 (JP-A-54-145,135).
Releasing a PUG by an intramolecular ring closure reaction of a p-nitrophenoxy derivative described in U.S. Pat.
Nos. 310,612 (JP-A-55-53,330) and 4,358,525, which release PUG by an intramolecular ring closure reaction after ring cleavage; US Pat. No. 4,330,617. Nos. 4,446,216, 4,483,919, JP-A-59-121,328, and the like, acid anhydrides by the intramolecular ring-closing reaction of the carboxyl group of the succinic acid monoester or its analogs. Release of PUG with the formation of a product; US Pat. No. 4,40
9,323, 4,421,845, Research Disclosure No. 21,228 (December 1981)
U.S. Pat. No. 4,416,977 (JP-A-57-57).
135,944), JP-A-58-209,736,
No. 58-209,738, which produces quinomonomethane or an analog thereof by electron transfer through a double bond conjugated with an aryloxy group or a heterocyclic oxy group to release PUG; US Pat. 4,420,5
54 (JP-A-57-136,640) and JP-A-57.
-135,945, 57-188,035, 5
8-98,728 and 58-209,737, which release PUG from the γ-position of enamine by electron transfer of the portion having the enamine structure of the nitrogen-containing heterocycle; JP-A-57-56, 837, which releases PUG by an intramolecular ring-closing reaction of an oxy group formed by electron transfer to a carbonyl group conjugated to a nitrogen atom of a nitrogen-containing heterocycle described in U.S. Pat. No. 4,146,396 52-90932), JP-A-59-93,442,
JP-A-59-75475, JP-A-60-249148
Releasing PUG with the formation of aldehydes described in JP-A No. 60-249149;
146, 828, 57-179, 842, 59
Those releasing PUG accompanied by decarboxylation of carboxyl group as described in JP -104,641; -O-COOCR _a R _b
-PUG (R _a and R _b represent a monovalent group), and is accompanied by decarboxylation and subsequent formation of aldehydes.
Those releasing UG; those releasing PUG with formation of isocyanate described in JP-A-60-7429; Oxidized products of color developing agents described in U.S. Pat. No. 4,438,193 and the like. And the like, which release PUG by a coupling reaction with These, Tim
Specific examples of the divalent linking group represented by e are JP-A 61-236,549 and JP-A 1,269,936.
And Japanese Patent Application No. 2-93,487.

General formulas (R-1), (R-2), (R-
In 3), PUG is a development inhibitor capable of reacting with the developer components and converting into a compound having less inhibitory properties when flowing out to the developer. Further, PUG has a hetero atom, and the general formulas (R-1), (R-2), (R-3) are introduced through the hetero atom.
It is bonded to the other part of the compound represented by. Examples of commonly known development inhibitors are described, for example, in The Theory of the Ph.D. Process by T. H. James.
otographic Process) ", 4th edition, 1977, published by Macmillan, 396-399 pages and Japanese Patent Application No. 2-
93,487, pages 56 to 69 and Japanese Patent Application No. 2-9.
No. 3,487, pages 56 to 69. These development inhibitors may have a substituent. Examples of useful substituents include mercapto group, nitro group, carboxyl group, sulfo group, phosphono group, hydroxy group,
Alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, amino group, acylamino group, sulfonylamino group, ureido group, urethane group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, A sulfonyl group,
Examples thereof include a sulfinyl group, a halogen atom, a cyano group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamidoki, and a phosphonamido group, and these groups may be further described. .. The PUG used in the present invention is an inhibitor capable of reacting with a developer component and converting into a compound having less inhibitory property when flowing out to a developer, and such a function among the known inhibitors is shown. Such a function can be imparted by using a development inhibitor which has been selected, or by combining the known inhibitor with a suitable substituent.

The development inhibitor represented by PUG used in the present invention is preferably a compound which inhibits nucleation infectious development. Nucleating and infectious development is performed by FUJIFILM GRANDEX system (Fuji Photo Film Co., Ltd.) or Kodak Ultratec.
This is a new development chemistry used in the image forming method of the system (Eastman Kodak Co., Ltd.). This development chemistry is described in "Journal of the Photographic Society of Japan" Vol. 52, No. 5, 390-390.
394 pages (1989) and "Journal of Photographic Science", 35 volumes, 162 pages (1987).
As described in, the development process of exposed silver halide grains by a conventional developing agent and the nucleation-active species based on the cross-oxidation between the oxidation product of the developing agent and the nucleating agent produced thereby. And the nucleation-infecting development process of the peripheral unexposed to weakly exposed silver halide grains by the active species. Therefore, the entire development process consists of the sum of the normal development process and the nucleation development process. Therefore, in addition to the normal development inhibitor conventionally known as a development inhibitor, a new nucleation-infectious development process is performed. A compound that suppresses can exert an inhibitory effect. The latter is referred to herein as a nucleation development inhibitor. The development inhibitor represented by PUG used in the present invention is preferably a nucleation development inhibitor. As the compound which acts as a nucleation development inhibitor, conventionally known development inhibitors are also effective, but particularly effective compounds include compounds having at least one or more nitro groups or nitroso groups, pyridine, pyrazine, A compound having a nitrogen-containing heterocyclic skeleton such as quinoline, quinoxaline, or phenazine, particularly a compound having a 6-membered nitrogen-containing heteroaromatic skeleton, a compound having an N-halogen bond, quinones, tetrazoliums, amine oxides, azoxy compounds, Examples thereof include coordination compounds having an oxidizing ability. Among them, a compound having a nitro group and a compound having a pyridine skeleton are particularly effective.

These nucleation development inhibitors may have a substituent, and the properties of the substituent, such as electron-withdrawing property, electron-donating property, hydrophobicity, hydrophilicity, adsorbability to charged silver halide, etc. Various properties such as the strength of development inhibition and the ease of diffusion can be controlled by the property of. Examples of useful substituents include those listed above as examples of common development inhibitor substituents. Specific examples of these nucleation development inhibitors useful in the present invention include Japanese Patent Application Nos. 2-258928, 2-258929 and 3-1.
5648 in detail. Further, as another series of nucleation development inhibitors, an adsorptive compound to a silver halide grain having an anionic charged group or a dissociative group capable of dissociating in a developing solution to generate anionic charge is also effective. ..

The nucleation development inhibitor as the PUG used in the present invention has a hetero atom and is bonded via the hetero atom of the general formulas (R-1), (R-2) and (R-3). It has a function of being released from the other part of the compound represented by the formula (3), and further has a function of reacting with the components of the developing solution and converting into a compound having less inhibitory property when flowing out to the developing solution. The PUG used in the present invention is preferably imparted with the above-mentioned two functions by bonding an appropriate substituent to a usual development inhibitor or a nucleation development inhibitor as shown in the specific examples, if necessary. When PUG used in the present invention flows out into the developer,
Although it reacts with the developer component and changes into a compound with less inhibitory properties, examples of such a developer component include alkali,
In addition to compounds such as hydroquinones and sulfite ions which are often contained in a developing solution, surfactants, amines, salts of organic acids and the like can be mentioned. For this purpose, special compounds such as fluoride ions, hydrazines, hydroxylamines and hydroxamic acids may be added to the developer, and the copying action of these components causes a change in PUG. Is also good. The PUG used in the present invention preferably has the following general formulas (P-1), (P-2) and (P-
It is represented by 3).

[0097]

[Chemical 46]

In the formula, X ₁ represents a trivalent organic group, and X ₂
Represents a group that reacts with a developing solution component to be converted into an anion group, and X ₃ represents a group that exhibits a nucleation development inhibiting effect. More specifically, X ₁ is an aliphatic group, an aromatic group, or these groups and -O-, -S-, -Se-,
—NR ₃ — (R ₃ represents a hydrogen atom, an aliphatic group or an aromatic group), —CO—, —SO—, a trivalent group formed by combining —SO ₂ — It may be replaced. Examples of preferred substituents are PU
Those listed as the substituents of G are applicable. The trivalent group represented by X ₁ in the general formula (P-1) is preferably the following general formulas (P-11), (P-12) and (P
-13). (However, it is expressed in the form including X ₂ and X ₃ in the general formula (P-1).)

[0099]

[Chemical 47]

In the formula, X ₂ and X ₃ have the same meanings as in formula (P-1). X ₁₁ represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle with a nitrogen atom. X ₁₂ and X ₁₃ represent a divalent organic group, and m and n represent 0 or 1. Preferably, X ₁₂ and X ₁₃ are an aliphatic group, an aromatic group, or these groups and —O—, —S—, —Se—, —NR ₃ — (R ₃
Is synonymous with general formula (P-1)), -CO-, -SO-,-.
It is a divalent group formed by combining SO ₂ — and may be substituted. As examples of preferable substituents, those enumerated as the substituents of PUG are applicable. In the general formula (P-11), the nitrogen-containing heterocycle formed by the nitrogen atom and X ₁₁ is preferably a heteroaromatic ring. Further, in the general formula (P-11), nitrogen atom and X ₁
The heteroaromatic ring group formed by is preferably a 5- to 6-membered ring, which may be a single ring or condensed with another ring, or may be substituted.

Representative examples of preferred heteroaromatic rings include, for example, pyrrole, imidazole, pyrazole, 1,2,
3-triazole, 1,2,4-triazole, tetrazole, 2-thioxathiazoline, 2-oxathiazoline, 2-thioxaxazoline, 2-oxoxazoline, 2-thioxaimidazoline, 2-oxaimidazoline, 3-thioxa -1,2,4-triazoline, 3-oxa-1,2,4-triazoline, 1,2-oxazoli-5-thione, 1,2-thiazoline-5-thione, 1,
2-oxazolin-5-one, 1,2-thiazoline-5
-One, 2-thioxa-1,3,4-thiadiazoline,
2-oxa-1,3,4-thiadiazoline, 2-thioxa-1,3,4-oxadiazoline, 2-oxa-1,
3,4-oxadiazoline, 2-thioxadihydropyridine, 2-oxadihydropyridine, 4-thioxadihydropyridine, 4-oxadihydropyridine, isoindole, indole, indazole, benzotriazole, benzimidazole, 2-thioxabenzimidazole, 2-oxabenzimidazole, benzoxazoline-2-thione, azaindenes, benzoxazoline-2-one, benzothiazoline-2-thione, benzothiazolin-2-one, carbazole, purine, carboline, phenoxazine, phenothiazine, various Pyrazolopyridines, pyrazolopyrimidines, pyrazolopyrroles, pyrazolopyrazoles, pyrazoloimidazoles, pyrazolooxazoles, pyrazolothiazoles, and pyrazolo in a condensed ring position Riazor acids, Imidazolopyrimidine pyridines, Imidazolopyrimidine pyrimidines, Imidazolopyrimidine pyrroles,
Examples thereof include imidazole imidazoles, imidazolooxazoles, imidazolothiazoles and imidazolotriazoles.

Further preferred heteroaromatic rings are, for example, pyrrole, imidazole, pyrazole, triazole,
Tetrazole, 2-thioxathiazoline, 2-thioxoxazoline, indole, indazole, benzotriazole, benzimidazole, 2-thioxa-1,
3,4-thiadiazoline, azaindene, 5-thioxa-tetrazoline, 2-thioxa-1,3,4-oxadiazoline, 3-thioxa-1,2,4-triazoline,
There are various condensed ring position pyrazolopyridines, pyrazoloimidazoles and the like, and particularly preferable are heteroaromatic rings having a pyrazole skeleton such as pyrazole, indazole and pyrazolopyridine. These heterocyclic compounds may have a substituent. Examples of the substituent include a mercapto group, a nitro group, a carboxyl group, a sulfo group, a phosphono group, a hydroxy group, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group and an acylamino group. Group, sulfonylamino group, ureido group, urethane group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, halogen atom, cyano group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group , Carbonamide group, sulfonamide group, phosphonamide group and the like.

[0103]

[Chemical 48]

In the formula, X ₂ and X ₃ have the same meaning as in the general formula (P-1), and X ₁₁ has the same meaning as in the general formula (P-11). X
₁₄ has the same meaning as X ₁ in formula (P-1).

[0105]

[Chemical 49]

In the formula, X ₂ and X ₃ have the same meanings as in the general formula (P-1), and X ₁₄ has the same meanings as in the general formula (P-12). X
₁₅ -O -, - S -, - Se -, - NR 3 - (R 3 is general formula (P-1) synonymous) represent. The group represented by X ₂ in the general formula (P-1) is a monovalent group that can be converted into an anionic functional group as a component of the developing solution. The change of X _{2 into} an anionic functional group is not a simple proton transfer such as dissociation of an acid with an alkali, but a change accompanied by the cleavage or formation of one or more covalent bonds due to the action of a developing solution component. Is preferable, and the generated anionic functional group is preferably in a state of being bonded to the portion represented by X ₁ in the general formula (P-1). It is also preferable that the conversion of X _{2 into} an anionic functional group occurs substantially after the PUG releasing reaction from the redox compound of the present invention. The group represented by X ₂ in the general formula (P-1) is preferably the following general formulas (P-14) to (P-1).
It is represented by 9).

[0107]

[Chemical 50]

In the formula, X ₂₁ is --COO--, --SO ₂ O--,-.
_{N (R 6) SO 2 O} -, - P (O) (OR) O- and represents, R ₄ represents a general formula _(R-1) R 1 and the definition of the group, R ₅ is a hydrogen atom or It represents a group having the same definition as R ₄ .

[0109]

[Chemical 51]

In the formula, X ₂₂ is --SO _2- , --CO--,-.
Represents (NHCO) _m −, and m is 1 or 2. R
₆ represents a group having the same definition as R _{4 in} formula (P-14) or a hydrogen atom, and three R ₆ may be the same or different.

[0111]

[Chemical 52]

In the formula, X ₂₃ represents —CO— or —SO ₂ — and X ₂₄ represents a monovalent group. The three X _{24 s} may be the same or different, and any two may be combined to form a ring. Formula _{(P-17) -SO 2 -CH} 2 CH in ₂ -X ₂₃ -X ₂₄ formula, X _23, X ₂₄ is same meaning as in formula (P-16)

[0113]

[Chemical 53]

In the formula, X ₂₅ represents a single bond, —O— or —NH—, and X ₂₆ represents Cl, OH or —NH ₂ . In the general formula _{(P-19) -X 25 -X} 23 -CH 2 -X 27 formula, X _23, X ₂₅ are each formula (P-16), a general formula (P-18) interchangeably, X ₂₇ represents halogen. In addition to the above, preferable examples of X ₂ include a formyl group, a —N═C═O group, and an oxirane group. Preferred examples of the group which exhibits the development inhibiting effect represented by X ₃ in the general formula (P-1) include a nitro group, a nitroso group, a nitrogen-containing heterocyclic group, a group having an N-halogen bond, and a quinone skeleton. Examples thereof include a group, a group having a tetrazolium skeleton, a group containing an amine oxide structure, a group containing an azoxy structure, and a group containing a coordination compound having an oxidizing ability. X ₃ is particularly preferably a nitro group, a nitroso group or a 6-membered nitrogen-containing heterocyclic group, most preferably a nitro group or a pyridyl group.

[0115] In the general formula _{(P-2) -Y 1 -Y} 2 -Y 3 Formula, Y ₁ represents a divalent organic group, Y ₂ is a divalent that can be cleaved by reaction with development processing solution components Represents a group, and Y ₃ represents a group exhibiting a nucleation development inhibiting effect. More specifically, Y ₁ is an aliphatic group, an aromatic group, or these groups and —O—, —S—, —Se—, —NR ₃ — (R ₃ has the same meaning as in formula (P-1). ), -CO-, -SO-, -S
It is a divalent group formed by combining O ₂ — and may be substituted. As examples of preferable substituents, those enumerated as the substituents of PUG are applicable. The divalent group represented by Y ₁ in the general formula (P-2) is preferably the following general formulas (P-21) and (P-2
It is represented by 2). (However, it is represented in the form including Y ₂ and Y ₃ in the general formula (P-2).)

[0116]

[Chemical 54]

In the formula, Y ₂ and Y ₃ have the same meanings as in formula (P-2). Y ₁₁ and Y ₁₂ have the same meanings as X ₁₁ and X _{12 in} formula (P-11), respectively, and the description of the preferred embodiments and the like applies to formula (P-11) as they are. 1 is 0 or 1. In the general formula _{(P-22) -Y 13 -Y} 12 -Y 2 -Y 3 Formula, Y _2, Y ₃ is general formula (P-2) in the above formula, Y
₁₂ has the same meaning as in formula (P-21). Y ₁₃ has the same meaning as X ₁₅ in formula (P-13).

In the redox compound of the present invention, PUG
Is represented by the general formula (P-2), the redox compound of the present invention is reacted with an oxidized product of a developing agent to yield Y ₁ -Y.
_2- Y ₃ is released, and the Y ₂ portion of Y ₁ -Y ₂ -Y ₃ is cleaved by the components of the developing solution. Here, it is preferable that the cleavage reaction of the Y ₂ portion occurs substantially later than the release reaction of Y ₁ -Y ₂ -Y ₃ . From this, the reaction of the divalent linking group represented by Time in the general formulas (R-1), (R-2) and (R-3) and the cleavage reaction of Y ₂ are easily mixed. However, in the reaction of Time, from the molecular combination of the redox compound of the present invention, Time-PU
The release of G is the main cause of the subsequent reaction of releasing PUG from Time-PUG (in other words, if Time-PUG is not released, PUG is not released substantially), while Y is released. The cleavage of ₂ occurs independently of the release of PUG (ie Time-Y ₁ -Y ₂
Without occur release -Y ₃ or Y ₁ -Y ₂ -Y _3, can occur cleavage of Y ₂ by the action of the developer components)
Preferably.

Further, by cleavage of Y ₂ , Y ₁ -Y _2-
If Y ₃ is represented as changes in Y ₁ -Y ₂₁ and Y ₂₂ -Y _3, Y ₂₂ preferably includes an anionic functional group, the anionic functional group is a functional group formed by cleavage of Y ₂ Preferably. More preferably Y ₂₂ is pK
It is preferable that a contains a conjugate base of an acidic functional group having 6 or less as a functional group, and particularly preferably contains a conjugate base of an acidic functional group having a pKa of 5 or less as a functional group. Preferable specific examples of these functional groups include a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphonic acid group, and a phosphinic acid group when expressed as an acidic functional group.

The group represented by Y ₂ in the general formula (P-2) is preferably the following general formulas (P-23) to (P-2).
It is represented by 6). (However, it is represented in the form including Y ₃ in the general formula (P-2).) In the general formula (P-23) —Y ₂₃ —Y ₂₄ —Y ₃ formula, Y ₃ is the general formula (P-2). And Y ₂₄ has the same meaning as X _{12 in} formula (P-11). Y ₂₃ is -OCO
-, - SCO -, - O -SO 2 -, - O-SO 2 N (R
_{3) -, - OP (O} ) (OR 3) - represents, R ₃ has the same meaning as in formula (P-1).

[0121]

[Chemical 55]

In the formula, Y ₃ has the same meaning as general formula (P-2) and Y ₂₄ has the same meaning as general formula (P-23). Y ₂₅ represents -CO- or -SO _2- , and Y ₂₆ represents -S-, -O- or -S.
Represents O ₂ −. Y ₂₇ represents a hydrogen atom or a monovalent group, and two Y ₂₇ may be the same or different and may bond to each other to form a ring. Further, either Y ₂₇ or two Y ₂₇ may combine with the group represented by Y ₁ in formula (P-2) to form a cyclic structure.

[0123]

[Chemical 56]

In the formula, Y ₃ , Y ₂₄ , Y ₂₅ , Y ₂₆ and Y ₂₇ have the same meanings as in formula (P-24).

[0125]

[Chemical 57]

In the formula, Y ₃ has the same meaning as in formula (P-2), Y ₂₄ has the same meaning as in formula (P-23), and Y ₂₅ and Y
₂₆ has the same meaning as in formula (P-24). Y ₂₈ represents a group of non-metal atoms necessary for forming a cyclic structure with a nitrogen atom, carbonyl and Y ₂₅ . For the description of the group represented by Y ₃ in formula (P-2), see formula (P-1).
The explanation of X _{3 in} the above is directly applied, and the preferable embodiments are also the same.

[0127]

[Chemical 58]

In the formula, Z _{1 to} Z ₅ represent a hydrogen atom or a monovalent group, and further satisfy at least one of the following conditions, conditions and conditions. At least one of the conditions Z ₂ and Z ₅ represents a nitro group. Conditions At least one of Z ₃ and Z ₄ is a nitro group, and at least two of Z _{1 to} Z ₅ are electron withdrawing groups. At least one of the conditions Z ₃ and Z ₄ is a nitro group, and Z ₁ is an aliphatic group or an aromatic group.

Explaining in more detail, examples of the monovalent group represented by Z _{1 to} Z ₅ include those listed as the substituent of R _{1 in} the general formula (R-1), a nitro group, a nitroso group and the like. Can be mentioned. When Z ₁ represents an aliphatic group, it is preferably a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 1 to 10 carbon atoms. It is also preferable that the alkyl group is substituted with an aryl group to be an aralkyl group having 7 to 10 carbon atoms. Specific examples include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a benzyl group and the like.
When Z ₁ represents an aromatic group, it preferably has 6 to 10 carbon atoms.
Or an unsaturated heterocyclic group having 5 to 10 carbon atoms, which may be substituted. As the examples of the substituent, those mentioned as examples of the monovalent group represented by Z _{1 to} Z ₅ are applicable. Specific examples of Z ₁ include a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, quinolyl group, isoquinolyl group and the like.

When Z _{2 to} Z ₅ represent at least two electron withdrawing groups (of which at least one represents a nitro group), the preferred electrowithdrawing group is the value of Hammett's substituent constant and σ _p is The substituent is 0.2 or more or σ _m is 0.3 or more, and particularly preferably the substituent is σ _p is 0.3 or more or σ _m is 0.4 or more. Specifically, nitro group, atinitro group, nitroso group, cyano group, trifluoromethyl group, polyhalogenated alkyl group such as trichloromethyl group, polyfluoroaryl group such as pentafluorophenyl group, alkyl or arylsulfonyl group,
An alkyl or arylsulfinyl group, a sulfamoyl group, a carbamoyl group, an alkyl or arylcarbonyl group, an alkyl or aryloxycarbonyl group,
Formyl group, arylazo group, amidino group, ammonio group, sulfonio group, acyloxy group, alkyl or arylsulfonyloxy group, phosphino group, phosphine oxide group, phosphonic acid ester group, phosphonic acid amide group, electron-deficient heterocyclic group, Examples thereof include bromine atom and fluorine atom. Further, these groups may be substituted, and examples of useful substituents include the general formula (R-
Those listed as examples of the substituent of R ₁ in 1) are mentioned. Further, it is preferable that any of Z ₂ , Z ₄ and Z ₅ is a nitro group, and it is particularly preferable that Z ₂ is a nitro group. Hereinafter, the general formula (P-
Specific examples of the PUG represented by 3) will be given, but the present invention is not limited thereto.

[0131]

[Chemical 59]

[0132]

[Chemical 60]

[0133]

[Chemical formula 61]

The general formulas (R-1), (R-2) and (R
-3), R ₁ or Time is a ballast group or a general formula (R-1), (R-2) or (R-3) commonly used in a non-moving photographic additive such as a coupler.
A group that promotes the adsorption of the compound represented by the formula (1) to silver halide may be incorporated. The ballast group is an organic compound giving a molecular weight sufficient to prevent the compounds represented by the general formulas (R-1), (R-2) and (R-3) from substantially diffusing into another layer or the treatment liquid. The group is composed of one or more combinations of alkyl groups, aryl groups, heterocyclic groups, ether groups, thioether groups, amide groups, ureido groups, urethane groups, sulfonamide groups, and the like.
The ballast group is preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

Specific examples of the adsorption-promoting group for silver halide include 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine,
Thiobarbituric acid, tetrazoline-5-thione, 1,
2,4-triazoline-3-thione, 1,3,4-oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3- Cyclic thioamide group such as imidazoline-2-thione, chain thioamide group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (If the carbon atom next to the -SH group is a nitrogen atom, It has the same meaning as a cyclic thioamide group in a tautomeric relationship, and specific examples of this group are the same as those listed above.), A group having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benz. Imidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, oki 5- or 6-membered nitrogen-containing heterocyclic group consisting of a combination of nitrogen, oxygen, sulfur and carbon, such as sol, oxazoline, thiadiazole, oxathiazole, triazine and azaindene, and heterocyclic quaternary compounds such as benzimidazolinium Examples include salt. These may be further substituted with appropriate substituents. Examples of the substituent include those mentioned as the substituent of R ₁ . Specific examples of the compound used in the present invention are listed below, but the present invention is not limited thereto.

[0136]

[Chemical formula 62]

[0137]

[Chemical 63]

[0138]

[Chemical 64]

[0139]

[Chemical 65]

[0140]

[Chemical 66]

[0141]

[Chemical 67]

[0142]

[Chemical 68]

[0143]

[Chemical 69]

[0144]

[Chemical 70]

[0145]

[Chemical 71]

[0146]

[Chemical 72]

[0147]

[Chemical 73]

[0148]

[Chemical 74]

As the redox compound used in the present invention, in addition to those described above, for example, Japanese Patent Application No. 2-258928.
Nos. 2-258929 and 3-15648 can be used. The method for synthesizing the redox compound used in the present invention is described in, for example, JP-A-61-21.
3,847, 62-260,153, U.S. Pat. No. 4,684,604, Japanese Patent Application No. 63-98,803,
U.S. Pat. Nos. 3,379,529 and 3,620,74
No. 6, No. 4,377, 634, No. 4,332, 878
JP-A-49-129,536, 56-153,
No. 336, No. 56-153,342, Japanese Patent Application No. 1-29
0,563, 2-62,337, 2-64,7
The method described in No. 17 or the like is helpful.

The redox compound of the present invention is used within the range of 1 × 10 ^{-6 to} 5 × 10 ^-2 mol, and more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, per mol of silver halide. .. The redox compound of the present invention is suitable for use in a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve and the like. It can be dissolved and used. Further, by a well-known emulsification and dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, by a method known as a solid dispersion method, the powder of the redox compound is ball milled in water, a colloid mill,
Alternatively, they can be dispersed by ultrasonic waves and used.

The silver halide emulsion used in the silver halide emulsion layer of the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide and silver iodochlorobromide. The emulsion is
It is preferable to contain a rhodium salt from the viewpoint of obtaining a super-high contrast image. For the rhodium salt content, it is desirable to select an optimum amount according to the grain size of the silver halide emulsion, the method and degree of chemical sensitization, etc., and the test method for the selection is well known to those skilled in the art. is there. Usually, preferably 1 × 10 ⁻⁸ mol to 1 × 1 mol per mol of silver halide.
It is used in the range of 0 ^-4 mol. Examples of the rhodium salt preferably used in the present invention include rhodium dichloride, rhodium trichloride, and rhodium ammonium hexachloride.

The average grain size of silver halide used in the present invention is preferably fine grains (for example, 0.7 μ or less), and particularly preferably 0.5 μ or less. The particle size distribution is basically not limited, but it is preferably monodisperse. Here, the monodisperse means that at least 95% by weight or the number of particles is composed of a particle group having a size within ± 40% of the average particle size.

The silver halide grains in the photographic emulsion are cubic,
It may have a regular crystal form such as an octahedron, or an irregular shape such as a sphere or a plate.
lar) crystal or a composite form of these crystal forms. The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases. Two or more kinds of silver halide emulsions formed separately may be mixed and used.

The emulsion layer of the present invention or the other hydrophilic colloid layer may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. As a filter dye, a dye for further reducing photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity region of silver halide, and safety against safelight light when handled as a light-sensitive material in a bright room 350 nm to 600 nm for increasing the
A dye having a substantial light absorption in the region is used. It depends on the molar extinction coefficient of the dye, but usually 10 ^-2 g / m ^{2 -1}
It is added in the range of g / m ² . Preferably 50 mg to 500
It is mg / m ² . Specific examples of dyes are described in JP-A-63-64039.
What is described in detail in the No. is used. The dye is dissolved in a suitable solvent [eg water, alcohol (eg methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof] for the non-photosensitive hydrophilic colloid layer of the present invention. It is added to the coating solution. These dyes can be used in combination of two or more. The dye of the present invention is used in an amount necessary to enable light room handling. The specific amount of the dye used is generally 10 ⁻³ g / m ^{2 to} 1 g / m ² , and particularly 10 ⁻³ g / m ^{2 to} 0.
A preferred amount can be found in the range of 5 g / m ² .

As the binder or protective colloid of the photographic emulsion, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-
N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole,
A wide variety of synthetic hydrophilic polymeric substances such as polyvinylpyrazole and other single or copolymers can be used. As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination for chemical sensitization. Good. The gold sensitization method is a typical one of the noble metal sensitization methods, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, platinum, palladium, iridium and other complex salts may be contained. A specific example is US Patent 2,
No. 448,060, British Patent No. 618,061 and the like. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines can be used in addition to the sulfur compounds contained in gelatin. As the reduction sensitizer, a primary tin salt, an amine, formamidinesulfinic acid, a silane compound or the like can be used.

A known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention. Specific examples of the spectral sensitizing dye are described in Japanese Patent Application No. 2-1263683, pp. 49-8.
5 and pages 77 to 124 of JP-A-62-215272.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during photographic processing or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptothiadiazoles, aminotriazoles,
Benzothiazoles, nitrobenzotriazoles, etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
3,3a, 7) Tetrazaindenes), pentaazaindenes, etc .; Add many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. be able to. Among these, preferred are benzotriazoles (eg 5-methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Further, these compounds may be contained in the treatment liquid.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chrome alum, etc.), aldehydes, (glutaraldehyde, etc.),
N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3
-Vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s
-Triazine, etc.), mucohalogen acids, etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced according to the present invention has a coating aid, an antistatic property, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic properties (for example, development acceleration). , Hardening, and sensitization), various surfactants may be included. For example, saponin (steroidal), alkylene oxide derivative (eg polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives ( Nonionic surfactants such as alkyl esters such as alkenyl succinic acid polyglyceride, alkylphenol polyglyceride, fatty acid esters of polyhydric alcohols, etc .; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyls Naphthalene sulfonate, alkyl sulfates, alkyl phosphates, N-acyl-N-alk Such as taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc., such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants containing acidic groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkylbetaines, amine oxides; alkylamine salts, aliphatic or aromatic primary surfactants. Quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. Also, JP-A-62-215272, pages 649 to 68
The compounds described on page 8 can be used.
Polymer latexes such as polyalkyl acrylates may be included for dimensional stability.

Development accelerators or accelerators for nucleating infectious development suitable for use in the present invention are described in JP-A-53-77.
616, ibid. 54-37732, ibid. 53-137, 13
In addition to the compounds disclosed in No. 3, No. 60-140, 340, No. 60-14959, etc., various compounds containing an N or S atom are effective. Next, specific examples will be listed.

[0162]

[Chemical 75]

[0163]

[Chemical 76]

[0164]

[Chemical 77]

The optimum addition amount of these accelerators varies depending on the kind of the compound, but 1.0 × 10 ^{−3 to} 0.5 g / m ² ,
It is preferably used in the range of 5.0 × 10 ^{−3 to} 0.1 g / m ² . These promoters are suitable solvents (H
₂ O) It is dissolved in alcohols such as methanol and ethanol, acetone, dimethylformamide, methylsolcerve, etc.) and added to the coating solution. Plural kinds of these additives may be used in combination.

In order to obtain ultrahigh contrast and high sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or pH 13 described in US Pat. No. 2,419,975 is used.
It is not necessary to use a highly alkaline developing solution close to the above, and a stable developing solution can be used. That is, the silver halide light-sensitive material of the present invention contains a sulfite ion as an accelerator of 0.
15 mol / liter or more, pH 10.5-12.
3, especially with a developing solution having a pH of 11.0 to 12.0, a sufficiently high-contrast negative image can be obtained. There is no particular limitation on the developing agent that can be used in the method of the present invention, and examples thereof include dihydroxybenzenes (for example, hydroquinone),
3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p
-Aminophenol) or the like can be used alone or in combination. The silver halide light-sensitive material of the present invention particularly contains dihydroxybenzenes as a main developing agent,
It is suitable for processing with a developer containing 3-pyrazolidones or aminophenols as an auxiliary developing agent.
In this developer, dihydroxybenzenes are preferably used in an amount of 0.05 to 0.5 mol / liter, and 3-pyrazolidones or aminophenols are used in an amount of 0.06 mol / liter or less. US Pat. No. 4,269,929
It is also possible to increase the developing speed and shorten the developing time by adding amines to the developing solution, as described in the publication. As the developer used in the present invention,
The amino compounds described in Japanese Patent Application No. 1-294185 can be used. Other developers include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles). Development inhibitor or antifoggant. Also, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant (particularly preferably the above-mentioned polyalkylene oxides), an antifoaming agent, a hardener, and a silver stain preventing agent for the film. (For example, 2-mercaptobenzimidazole sulfonic acids, etc.) may be included.
As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt or the like as a hardening agent.

The processing temperature in the method of the present invention is usually 18
It is selected between 0 ° C and 50 ° C. Although it is preferable to use an automatic processor for photographic processing, even if the total processing time from putting the light-sensitive material in the automatic developing machine until it comes out is set to 60 seconds to 120 seconds by the method of the present invention. The photographic characteristics of a super gradation of negative gradation can be obtained. The compounds described in JP-A-56-24,347 can be used in the developer of the present invention as a silver stain preventing agent. The compounds described in JP-A-61-267759 can be used as dissolution aids added to the developing solution. Furthermore, the pH used for the developer
As the buffer agent, the compounds described in JP-A-60-93,433 or the compounds described in JP-A-62-186259 can be used.

[0168]

【Example】

Example 1 <Preparation of Silver Halide Emulsion> Emulsion-A 0.37 mol of silver nitrate aqueous solution and (NH ₄ ) ₃ RhCl corresponding to 1.0 × 10 ⁻⁷ mol per 1 mol of silver in the finished emulsion.
_An aqueous halogen salt solution containing ₆ and 2 × 10 ⁻⁷ mol of K ₃ IrCl ₆ , 0.11 mol of potassium bromide and 0.27 mol of sodium chloride, sodium chloride and 1,3-dimethyl-2-imidazolidinethione. Nucleation is carried out by adding a double jet method at 45 ° C. for 12 minutes to an aqueous solution of gelatin containing the above to obtain silver chlorobromide grains having an average grain size of 0.20 μm and a silver chloride content of 70 mol%. It was Then, similarly, a 0.63 mol silver nitrate aqueous solution, a 0.19 mol potassium bromide, and a 0.47 mol sodium chloride containing halogen salt aqueous solution were added by the double jet method over 20 minutes. Thereafter, 1 × 10 ⁻³ mol of KI solution was added per mol of silver, conversion was carried out, and the product was washed with water by a flocculation method in accordance with a conventional method, 40 g of gelatin was added, pH 6.5, pAg 7.5.
The amount of sodium benzenethiosulfonate (7 mg), sodium thiosulfate (5 mg) and chloroauric acid (8 mg) were added per 1 mol of silver, and the mixture was heated at 60 ° C. for 45 minutes to be chemically sensitized. 150 mg of 3a, 7-tetrazaindene and proxel as a preservative were added. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation 9%)

(Preparation of Coating Sample) On a polyethylene terephthalate film (150 μ) support having an undercoat layer (0.5 μ) made of a vinylidene chloride copolymer, UL, EM and PC were sequentially coated from the support side. Sample No. is applied so that it has a layered structure. 101-111 were created. The preparation method and coating amount of each layer are shown below. (UL) 10 g of gelatin, 20 wt% of polyethyl acrylate with respect to gelatin, 2 wt% of compound (a) with respect to gelatin were added, and water was added to a final amount of 250 ml to prepare 0.5 g of gelatin. It was applied so as to be / m ² . (EM) The above emulsion-A was dissolved at 40 ° C. together with gelatin, and the following compound S-1 was used as a sensitizing dye in an amount of 3.6 × 1.
0 ^-4 mol / mol Ag of 5-methyl benzotriazole 6.5 mg / m ^2, 4-hydroxy-1,3,3a, 7- tetrazaindene 1.3 mg / m ^2, 1-phenyl-5-mercaptotetrazole 1 mg / m ² , the following compound (a) 50 mg
/ M ² , 15 wt% polyethyl acrylate with respect to gelatin, 15 wt% with respect to gelatin the following compound (c),
As a gelatin hardening agent, 4 wt% of the following compound (b) with respect to gelatin, and the nucleating agent of the general formula (N-1) of the present invention and the general formula (Q-1) and the general formula (Q-2) The compounds were added as shown in Table 2 and coated so as to have Ag of 3.6 g / m ² .

[0170]

[Chemical 78]

[0171]

[Chemical 79]

Polymethylmethacrylate dispersion (average particle size 5 μm) and the following surfactants (d, h, f) were added to (PC) gelatin solution, and gelatin 0.5 g /
m ^2, and was applied as a 0.5 g / m ² as polymethylmethacrylate.

[0173]

[Chemical 80]

The back layer was coated according to the following formulation. [Back layer formulation] Gelatin 4 g / m ² Matting agent Polymethylmethacrylate (particle size 3.0 to 4.0 µ) 10 mg / m ² Latex Polyethyl acrylate 2 g / m ² Surfactant p-Dodecylbenzenesulfonic acid sodium 40 mg / M ² Fluorine-based surfactant (f) 5 mg / m ² gelatin hardening agent; Compound (b) 110 mg / m ² Dye Mixture of dyes [a], [b], [c] and [d] Dye [a] 53 mg / m ² dye [b] 14 mg / m ² dye [c] 25 mg / m ² dye [d] 18 mg / m ²

[0175]

[Chemical 81]

[0176]

[Chemical formula 82]

[0177]

[Chemical 83]

Table 1 shows the formulation of the developing solution used in this example.

[0179]

[Table 1]

Table 2 shows the amount of the nucleating agent used in the EM in this example, the amount of the compound of the general formulas (Q-1) and (Q-2), and the photographic results when these were used. ..

[0181]

[Table 2]

From the results shown in Table 2, when the nucleating agent of the present invention and the general formula (Q-1) or (Q-2) are used, the photographic characteristics are not significantly changed, black spots are very small, and after the thermostat You can see that they are maintaining a very low level. On the other hand, sample Nos. Using comparative compounds a, b, and c. 109-11
In 1, in Fresh, in particular N using comparative compounds b and c
o. Although 110 and 111 have the effect of reducing black spots, they are much larger than the present invention. According to the present invention, a photographic light-sensitive material having few black spots can be obtained without significantly changing photographic characteristics.

Example-2 The nucleating agent for EM of Example-1 was used as Compound Example I-5) 2.5 ×.
10 ⁻⁵ mol / m ² , I-20) 2.5 × 10 ⁻⁷ mol / m ² and the general formula (Q-1), (Q-
A sample was prepared in the same manner as in Example-1 except that the compound of 2) was added, and an exposure treatment was carried out in the same manner as in Example-1. The results are shown in Table-3.

[0184]

[Table 3]

As is clear from the results shown in Table 3, the compounds of the general formulas (Q-1) and (Q-2) of the present invention have an effect of suppressing black spots even when added to the UL layer. I understand.

Example-3 Emulsion-B Same as Emulsion-A except that (NH ₄ ) ₃ RhCl ₆ in Emulsion-A above was changed to 1.8 × 10 ⁻⁷ per mol of silver in the finished emulsion. Was prepared.

(Preparation of Coating Sample) On a polyethylene terephthalate film (150 μ) support having an undercoat layer (0.5 μ) made of a vinylidene chloride copolymer, UL, EMU, ML, in order from the support side. Sample No. was applied so as to have a layer structure of EMO and PC. Nos. 301 to 312 were created. The preparation method and coating amount of each layer are shown below. (UL) 10 g of gelatin, 20 wt% of polyethyl acrylate with respect to gelatin, 2 wt% of compound (a) with respect to gelatin were added, and water was added to a final amount of 250 ml to prepare 0.5 g of gelatin. It was applied so as to be / m ² . (EMU) The emulsion-A was dissolved with gelatin at 40 ° C., and the compound S-1 of Example-1 was used as a sensitizing dye in an amount of 3.6 × 10 ⁻⁴ mol / mol Ag, 5-methylbenztriazole 6 0.5 mg / m ² , 4-hydroxy-1,3,3
a, 7-Tetrazaindene 1.3 mg / m ² , 1-phenyl, 5-mercaptotetrazole 1 mg / m ² , Example-1
Compound (a) of 50 mg / m ² , 15 wt% with respect to gelatin
15% by weight of polyethyl acrylate and gelatin
As the compound (c) of Example-1 of Example 1 and a gelatin hardening agent,
4 wt% of the compound of Example-1 (b) based on gelatin,
The nucleating agent (I-5) of the present invention 3.8 × 10 ⁻⁵ mol / m ² and the compounds of the general formulas (Q-1) and (Q-2) of the present invention were added as shown in Table 4. Then, it was applied so as to have Ag of 3.6 g / m ² . (ML) 10 g of gelatin, 20 wt% of polyethyl acrylate with respect to gelatin, 2 wt% of the compound (a) with respect to gelatin were added, and water was added to a final amount of 250 ml to prepare gelatin 1. It was applied so as to be 0 g / m ² . (EMO) After dissolving the emulsion-B together with gelatin,
The compound S-1 as a sensitizing dye is 3.6 × 10 ⁻⁴ mol / mol Ag, 4-hydroxy-1,3,3a, 7-tetrazaindene 1.0 mg / m ² , which is oxidized according to the present invention. As a result, a compound releasing a development inhibitor was added as shown in Table 4, and the compound (a) was 20 mg / m ² , and the amount was ² with respect to gelatin.
0 wt% of polyethyl acrylate, and as a gelatin hardener, said compound of 4 wt% of (b) was added to the gelatin, Ag0.4g / m ^2, was coated as a gelatin 0.4 g / m ² .. (PC) Gelatin solution in polymethylmethacrylate dispersion (average particle size 5μ), and the surfactant (d,
E, f) is added and gelatin 0.5 g / m ^2, was coated as a 0.5 g / m ² as polymethylmethacrylate. The back layer was applied according to the following formulation. [Back layer formulation] Gelatin 4 g / m ² matting agent Polymethylmethacrylate (particle size 3.0 to 4.0 μ) 10 mg / m ² latex Polyethyl acrylate 2 g / m ² Surfactant p-dodecylbenzene sulfonic acid sodium 40 mg / M ² Fluorine-based surfactant (f) 5 mg / m ² gelatin hardening agent; Compound (b) 110 mg / m ² Dye Mixture of dyes [a], [b], [c] and [d] Dye [a] 53 mg / m ² dye [b] 14 mg / m ² dye [c] 25 mg / m ² dye [d] 18 mg / m ² Compounds (a) to (f) and dye (a) to (used in this example. d) is exactly the same as the compound shown in Example-1.

The developing solution used in this example is the same as that in Example-1.

Performance evaluation was performed in the same manner as in Example-1. The results are shown in Table 4.

[0190]

[Table 4]

From the results shown in Table 4, the use of the nucleating agent of the present invention and the general formulas (Q-1) and (Q-2) together can suppress the generation of black spots. Even when the redox compound of the present invention is used in the EMO layer, by using the nucleating agent of the present invention and the general formulas (Q-1) and (Q-2) in combination, sufficient effect for suppressing black spots can be obtained. It turns out that there is.

Example 4 (Preparation of Photosensitive Emulsion) An aqueous gelatin solution kept at 59 ° C. contained 5.0 × 10 ⁻⁶ mol of (NH ₄ ) ₃ RHCl per mol of silver.
After simultaneously mixing an aqueous solution of silver nitrate and an aqueous solution of sodium chloride in the presence of ₆ , gelatin was added after removing soluble salts by a method well known in the art, and as a stabilizer without chemical ripening. Methyl-4-hydroxy-1,
3,3a, 7-Tetrazaindene was added. This emulsion was a cubic-shaped monodisperse emulsion having an average size of 0.15μ. (Emulsion A) Emulsion B was prepared in the same manner as emulsion A except that (NH ₄ ) ₃ RhCl ₆ in emulsion-A was changed to 8.3 × 10 ^-6 mol. (Preparation of coating sample) Support; polyethylene terephthalate film (150μ) having an undercoat layer (0.5μ) made of vinylidene chloride copolymer. This support was coated from the support layer so as to have a layer structure of UL, EMU, ML, EMO, and PC. The preparation method and coating amount of each layer are shown below. The compound (d) was added to a 3% aqueous solution of (UL) gelatin, and the mixture was coated at 0.3 g / m ² as gelatin. The amount of compound (d) was 10 mg / m ² . (EMU) The above emulsion (A) was redissolved, polymer particles containing a hydrazine derivative were added, and further, the following compounds (a) to (d) and 30 wt% of polyethyl acrylate with respect to gelatin and a hardener were used. , 1,3-vinylsulfonyl-propanol (2 wt% to gelatin) was added to prepare, Ag3.8g / m ^2, gelatin 2 g / m ^2, nucleating agent I-5 as a 7.5 × 10 ^-5 mol It was applied so that it would be / m ² .

[0193]

[Chemical 84]

(ML) Gelatin (10 g) was dissolved in an aqueous solution containing 0.12% of the compound (d) to give a final amount of 300.
It was prepared so that the amount would be 1.0 ml / ml and gelatin was applied so as to be 1.0 g / m ² . (EMO) The compound (R-3) capable of releasing the development inhibitor by re-dissolving the emulsion (B) and oxidizing the compound (R-3) is added in an amount of 7.5 × 10 ⁻⁵ mol / m ² , and further the compound (a). ) 0.0
3 mg / m ² , and prepared by adding 30 wt% of polyethyl acrylate to gelatin and 1,3-vinylsulfonyl-2-propanol (2 wt% to gelatin) as a hardening agent, Ag 0.3 g / m ² , Gelatin at 0.4 g / m ² were applied. Polymethylmethacrylate particles (average particle size 2.5 μm) were added as a matting agent to a (PC) gelatin solution, and the following surfactants (e) and (f) were added as coating aids.
(G), stabilizer (h), (i), and ultraviolet absorber (j) were added and prepared, and gelatin was applied at 1.5 g / m ² and matting agent at 0.3 g / m ² . ..

[0195]

[Chemical 85]

(Preparation Method of Polymer Fine Particles Containing Nucleating Agent)
A solution comprising 1.5 g of nucleating agent I-5, 3.0 g of I-30, 1.7 g of melting point depressant (A-1), 6.0 g of poly (t) butyl acrylamide, and 50 ml of ethyl acetate was heated to 60 ° C. After heating, the mixture was added to 120 ml of an aqueous solution containing 12 g of gelatin, 0.7 g of sodium dodecylbenzenesulfonate and 20 mg of proxel, and a high-speed stirrer (homogenizer, manufactured by Nippon Seiki Seisakusho) was used to obtain a fine particle emulsion. Ethyl acetate was removed from this emulsion by heating under reduced pressure.
The average particle size of the emulsion was 0.13 μm.

[0197]

[Chemical formula 86]

The compound of the present invention (Q-
1) and (Q-2) were added as shown in Table 5, and sample No.
401-405 were created.

This sample was measured with a bright room printer p-607 manufactured by Dainippon Screen Co., Ltd. using the method disclosed in JP-A-2-293736.
Image exposure through a document as shown in FIG.
After development at 8 ° C. for 20 seconds, fixing, washing with water, and drying, the image quality of extracted characters was evaluated. The image quality of blank characters 5 is 30 μm when properly exposed so that a halftone dot area of 50% becomes 50% of halftone dot area on the return light-sensitive material using the original as shown in FIG.
It is the image quality with which characters with a wide width are reproduced, and it is a very good character quality with blank characters. On the other hand, the extracted character image quality 1 is an unexplained extracted character quality, which is an image quality that can reproduce only characters having a width of 150 μm or more when the same appropriate exposure is given, and is between 4 and 2 in the sensory evaluation between 5 and 1. Rank is set. A level of 3 or more is a practical level. The results are shown in Table 3. The sample of the present invention is excellent in extracted character image quality.

[0200]

[Table 5]

From the results of Table 5, the sample No. of the present invention was obtained. 402
At 405, the halftone dot quality is excellent, black spots are extremely small, and good photographic properties are obtained.

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[Chemical formula 61]

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[0168]

Example 1 <How to make a silver halide emulsion> Emulsion-A 0.37 mol of an aqueous silver nitrate solution, and 1.0 × 10 ⁻⁷ mol per mol of silver of the finished emulsion (NH ₄ ) ₃ Rh
Cl ₆ and 2 × 10 ⁻⁷ mol of K ₃ IrCl ₆ , 0.11
An aqueous halogen salt solution containing 1 mol of potassium bromide and 0.27 mol of sodium chloride was added to
To obtain silver chlorobromide grains having an average grain size of 0.20 μm and a silver chloride content of 70 mol% by adding to a gelatin aqueous solution containing dimethyl-2-imidazolidinethione by stirring at 45 ° C. for 12 minutes by a double jet method. Nucleation was performed by. Then, similarly, a 0.63 mol silver nitrate aqueous solution, a 0.19 mol potassium bromide, and a 0.47 mol sodium chloride containing halogen salt aqueous solution were added by the double jet method over 20 minutes. Then silver 1
Conversion was carried out by adding 1 × 10 ⁻³ mol of KI solution per mol, followed by washing with water by the flocculation method according to a conventional method, adding 40 g of gelatin, pH 6.5, pA
g 7.5, sodium benzenethiosulfonate 7 mg, sodium thiosulfate 5 mg and chloroauric acid 8 mg were added per 1 mol of silver, and the mixture was heated at 60 ° C. for 45 minutes for chemical sensitization treatment, and then added as a stabilizer. 150 mg of -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and proxel as preservative were added. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation 9%)

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[Chemical 78]

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[Chemical 79]

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[0176]

[Chemical formula 82]

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[0181]

[Table 2]

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(Preparation of Coating Sample) On a polyethylene terephthalate film (150 μ) support having an undercoat layer (0.5 μ) made of a vinylidene chloride copolymer, UL, EMU, ML, in order from the support side. Sample No. 1 was applied so as to have a layer structure of EMO and PC. 301 to 312
It was created. The preparation method and coating amount of each layer are shown below. (UL) Gelatin 10 g, 20 wt% with respect to gelatin
2 wt% of the polyethyl acrylate and the compound (ii) were added to gelatin, and water was added to the final amount of 250 ml to prepare gelatin, and the gelatin was applied to 0.5 g / m ² . (EMU) The emulsion-A was dissolved at 40 ° C. together with gelatin, and then the compound S-1 of Example-1 was used as a sensitizing dye in an amount of 3.6 × 10 ⁻⁴ mol / mol Ag, 5-methylbenztriazole 6 0.5 mg / m ² , 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene 1.3 mg /
m ² , 1-phenyl, 5-mercaptotetrazole 1 m
g / m ² , the compound (a) of Example-1 50 mg / m ² ,
15 wt% of polyethyl acrylate to gelatin, 15 wt% of compound of Example-1 (c) to gelatin, and 4 w of gelatin as a gelatin hardening agent.
t% of the compound of Example-1 (b), the nucleating agent of the present invention (I
-5) 3.8 × 10 ⁻⁵ mol / m ² and compounds of the general formulas (Q-1) and (Q-2) of the present invention were added as shown in Table 4 to obtain Ag of 3.6 g / m 2. ^It was applied so as to be ² . (ML) 10 g of gelatin, 20% by weight of polyethyl acrylate to gelatin, 2 wt% of the compound (a) to gelatin were added, and water was added to a final amount of 250 ml to prepare gelatin 1. It was applied so as to be 0 g / m ² . (EMO) After dissolving the emulsion-B together with gelatin,
The compound S-1 was used as a sensitizing dye in an amount of 3.6 × 10 ⁻⁴ mol / mol Ag, 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene 1.0 mg / m ² , the compound of the present invention which releases a development inhibitor upon oxidation is added as shown in Table 4, the compound (a) 20 mg / m 2
² , 20 wt% of polyethyl acrylate to gelatin, and 4 to gelatin as a gelatin hardening agent
Add 0.4 wt% of the above compound (b)
m ² and gelatin were applied at 0.4 g / m ² . (PC) Gelatin solution in polymethylmethacrylate dispersion (average particle size 5μ), and the surfactant (d,
E, f) is added and gelatin 0.5 g / ^{m 2,} was coated as a 0.5 g / ^{m 2} as polymethylmethacrylate. The back layer was applied according to the following formulation. [Back layer formulation] Gelatin 4 g / m ² Matting agent Polymethylmethacrylate (particle diameter 3.0 to 4.0 µ) 10 mg / m ² latex Polyethyl acrylate 2 g / m ² Surfactant p-dodecylbenzene sulfonate sodium 40 mg / M ² Fluorine-based surfactant (f) 5 mg / m ² gelatin hardening agent; Compound (b) 110 mg / m ² Dye Mixture of dyes [a], [b], [c] and [d] Dye [a] 53 mg / m ² dye [b] 14 mg / m ² dye [c] 25 mg / m ² dye [d] 18 mg / m ² Compounds (a) to (f) and dyes (a) to (used in this example. d) is exactly the same as the compound shown in Example-1.

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Example 4 (Preparation of Photosensitive Emulsion) An aqueous gelatin solution maintained at 59 ° C. contained 5.0 × 10 ⁻⁶ mol of (NH ₄ ) ₃ RH per mol of silver.
An aqueous solution of silver nitrate and an aqueous solution of sodium chloride were simultaneously mixed in the presence of Cl ₆ , and a soluble salt was removed by a method well known in the art, and then gelatin was added to the mixture as a stabilizer without chemical ripening. -Methyl-4-hydroxy-
1,3,3a, 7-Tetrazaindene was added. This emulsion was a cubic-shaped monodisperse emulsion having an average size of 0.15μ. (Emulsion A) (NH ₄ ) ₃ RhCl ₆ of Emulsion-A was added to 8.3 × 10 ^−6.
Emulsion B was prepared in exactly the same manner as Emulsion A, except that the molar amount was changed. (Preparation of coating sample) Support; polyethylene terephthalate film (150μ) having an undercoat layer (0.5μ) made of vinylidene chloride copolymer. This support was coated from the support layer so as to have a layer structure of UL, EMU, ML, EMO, and PC. The preparation method and coating amount of each layer are shown below. The compound (d) was added to a 3% aqueous solution of (UL) gelatin, and the mixture was coated at 0.3 g / m ² as gelatin. The amount of compound (d) was 10 mg / m ² . (EMU) The above emulsion (A) was redissolved, polymer particles containing a hydrazine derivative were added, and further the following compounds (a) to (d) and 30 wt% of polyethyl acrylate to gelatin and a hardener were added. , 1,3-bisvinylsulfonyl 2-propanol (2 wt% to gelatin) were added to prepare Ag 3.8 g / m ² , gelatin 2.
g / m ² , 7.5 × 10 ⁻⁵ mol as nucleating agent I-5
It was applied so as to be / m ² .

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(ML) 10 g of gelatin was dissolved in an aqueous solution containing 0.12% of the compound (d) to obtain a final amount of 300
It was prepared so as to have a volume of ml, and coated so that the amount of gelatin would be 1.0 g / m ² . (EMO) The compound (R-3) capable of releasing the development inhibitor by re-dissolving the emulsion (B) and being oxidized, is added to 7.5 × 10 ⁻⁵ mol / m ² , and further the compound (a) )
0.03 mg / m ² , and 30 wt% with respect to gelatin
As polyethyl acrylate and hardener of 1,3-
Added bis vinylsulfonyl-2-propanol (2 wt% to gelatin) were prepared, Ag0.3g / ^{m 2,} was coated as a gelatin 0.4 g / ^{m 2.} Polymethylmethacrylate particles (average particle size 2.5 μm) were added as a matting agent to a (PC) gelatin solution, and the following surfactants (e) and (f) were added as coating aids.
(G), stabilizer (h), (i), and ultraviolet absorber (j) were added and prepared, and gelatin was applied at 1.5 g / m ² and matting agent at 0.3 g / m ² . ..

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazumi Arai 210 Nakanishuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (2)

[Claims] 1. A support having a silver halide emulsion layer containing at least one nucleating agent represented by the general formula (N-1), the silver halide emulsion layer and / or a halogen adjacent thereto. A silver halide photographic light-sensitive material characterized in that a hydrophilic colloid layer containing no silver halide emulsion contains at least one compound selected from compounds represented by formulas (Q-1) and (Q-2). .. General formula (N-1): In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amino group, a hydrazino group, a carbamoyl group or an oxycarbonyl group, and G ₁ represents -C (O)-group,-
SO ₂ - group, -SO- group, -P (= O) (R 2) - group,
Represents a —COCO— group, a —CS— group or an iminomethylene group, and A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group Represents a group or a substituted or unsubstituted acyl group. General formula (Q-1) In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and Z represents an atomic group necessary for forming a nitrogen-containing heterocyclic aromatic ring. General formula (Q-2): In the formula, R represents an aromatic group, and B represents a phenyl group or a naphthyl group. 2. A silver halide photographic light-sensitive material comprising a support, a first silver halide emulsion layer, a hydrophilic colloid layer, a second silver halide emulsion layer, and a protective layer, which are sequentially coated in this order. In the material, or in the silver halide emulsion layer containing the nucleating agent represented by the following general formula (N-1) and not containing the nucleating agent, the following general formula (R-1),
A silver halide emulsion layer containing at least one redox compound represented by the general formula (R-2) and the general formula (R-3) capable of releasing a development inhibitor by being oxidized and containing a nucleating agent; And / or a hydrophilic colloid layer containing no silver halide emulsion adjacent thereto containing at least one of the compounds represented by the general formula (Q-1) and the general formula (Q-2). Silver halide photographic light-sensitive material. General formula (N-1): In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amino group, a hydrazino group, a carbamoyl group or an oxycarbonyl group, and G ₁ represents -C (O)-group,-
SO ₂ - group, -SO- group, -P (= O) (R 2) - group,
Represents a —COCO— group, a —CS— group or an iminomethylene group, and A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group Represents a group or a substituted or unsubstituted acyl group. General formula (Q-1): In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group, and Z represents an atomic group necessary for forming a nitrogen-containing heterocyclic aromatic ring. General formula (Q-2): In the formula, R represents an aromatic group, and B represents a phenyl group or a naphthyl group. [Chemical 7] In these formulas, R ₁ represents an aliphatic group or an aromatic group.
G ₁ is -CO- group, -COCO- group, -CS- group, -C
(= NG ₂ R ₂₎ - represents the group - group, -SO- group, -SO ₂ - group or _{-P (O) (G 2 R} 2). G ₂ represents a mere bond, —O— group, —S— group or —N (R ₂ ) — group, R ₂ represents a group having the same definition as R ₁ or a hydrogen atom, and a plurality of R's are present in the molecule. _{If two} are present they may be the same or different. A ₁ and A ₂ represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. In the general formula (R-1), at least one of A ₁ and A ₂ is a hydrogen atom. A ₃
Is synonymous with A ₁ or —CH ₂ CH (A ₄ ) — (Tim
e) represents _t- PUG. A ₄ is a nitro group, a cyano group,
Carboxyl group, a sulfonyl group or -G ₁ -G ₂ -R
₁ (in this case, two -G ₁ -G ₂ -R ₁ in the molecule may be the same or different). Time represents a divalent linking group, and t represents 0 or 1. PU
G represents a development inhibitor capable of reacting with the components of the developer and converting into a compound having less inhibitory properties when flowing out to the developer.